Sensory coding and the second spectra of natural signals

Natural auditory and visual stimuli are shown to demonstrate consistent non-Gaussian signatures: their phase-only second spectra behave approximately as the inverse square root of frequency, a property which is due to a predominance of difference beats between Fourier components at slightly offset frequencies. These second spectra also demonstrate statistical scale invariance, a hypothesis which is tested explicitly by computing phase-only second spectra from bandpass-filtered data. The bandpass frequency selectivity observed experimentally in sensory cells is shown to be qualitatively consistent with a strategy of exploiting the non-Gaussian structure of natural signals.     

A preservation study of carbon nanotubes in alumina-based nanocomposites via Raman spectroscopy and nuclear magnetic resonance

Raman spectroscopy was used to study the preservation of the carbon nanotube structure in nanotube-reinforced alumina nanocomposites consolidated via spark plasma sintering (SPS). A series of Raman spectroscopy experiments was used to identify the thermal breakdown temperature of single-walled carbon nanotubes (SWCNTs) embedded in nanocrystalline alumina. It was found that the carbon nanotube structure remains intact after sintering at 1150 °C, but almost completely breaks down by 1350 °C after only 5 min. Also, ²⁷Al nuclear magnetic resonance (NMR) was used to study the chemical and structural effects of high-energy ball milling (HEBM) and SPS consolidation on pure alumina and SWCNT-alumina nanocomposites. HEBM does not change the mixed coordination number of the as-received alumina, but slight peak shifts indicate residual stresses. No Al₄C₃ was detected in any of the consolidated samples – even up to 1550 °C for 10 min. Thus, it is concluded that consolidation of carbon nanotube-reinforced composites should be completed at temperatures below ∼1250 °C in order to preserve the carbon nanotube structure. PACS 61.18.Fs; 61.46.Fg; 61.82.Rx; 62.25.+g; 76.60.-k     

Numerical simulation aided relative optical density analysis of TEM images for soot morphology determination

The relative optical density (ROD) method provides a means to measure three-dimensional information about soot aggregates from two-dimensional transmission electron microscopy (TEM) micrographs of soot. The method is dependent on accurate calibration of the relationship between the measured soot ROD in TEM images and the actual soot thickness perpendicular to the imaging plane. A novel calibration method based on the comparison between probability distributions of measured soot ROD in TEM images and that of virtual soot thickness of numerically simulated soot is introduced. Soot aggregates of various prescribed fractal structure parameters were numerically generated using a tunable cluster-cluster aggregation model. The probability histograms of the local soot thickness for the simulated soot aggregates and ROD of the TEM images of flame generated soot aggregates were found to be quite similar and were used as a basis to establish a quantitative relationship between ROD and the local soot thickness. The calibration constant obtained from the analysis of the simulated soot was found to be insensitive to the fractal structure parameters over a wide range. The calibrated ROD method is successfully applied to the morphology analysis of soot aggregates generated in an atmospheric laminar co-flow ethylene-air diffusion flame based on thermophoretic sampling (TS) and TEM analysis techniques. With the ROD method, an overlap coefficient is introduced to identify and eliminate non-soot-aggregate structures and the selection of a cut-off overlap coefficient was found to have little influence on the final results over a relatively wide range. ROD is independent of empirical constants and human judgments and has been found to be an accurate and reliable TEM image analysis method for studying the morphology of soot aggregates.     

Trading N and O. Part 4: Asymmetric synthesis of syn-β-substituted-α-amino acids

A total of nine enantiopure syn-β-substituted-α-amino acids have been synthesised, comprising both syn-β-hydroxy-α-amino acids and syn-β-fluoro-α-amino acids. The key step in the synthetic strategy towards these syn-β-substituted-α-amino acids involves a stereospecific rearrangement, which proceeds via the intermediacy of the corresponding aziridinium ions. The requisite enantiopure syn-α-hydroxy-β-amino esters were prepared via asymmetric aminohydroxylation of the corresponding α,β-unsaturated esters followed by epimerisation of the resultant anti-α-hydroxy-β-amino esters at the C(2)-position. Subsequent activation of the α-hydroxy moiety as a leaving group followed by displacement by the β-amino substituent gave the corresponding aziridinium species. Regioselective in situ ring-opening of the aziridinium intermediates with either water or fluoride gave the corresponding syn-β-hydroxy-α-amino ester or syn-β-fluoro-α-amino ester, respectively, and N-deprotection and ester hydrolysis afforded the target syn-β-substituted-α-amino acids as single diastereoisomers in good overall yield.     

Catalytic Enantioselective Direct Aldol Addition of Aryl Ketones to α-Fluorinated Ketones

The catalytic enantioselective synthesis of α-fluorinated chiral tertiary alcohols from (hetero)aryl methyl ketones is described. The use of a bifunctional iminophosphorane (BIMP) superbase was found to facilitate direct aldol addition by providing the strong Brønsted basicity required for rapid aryl enolate formation. The new synthetic protocol is easy to perform and tolerates a broad range of functionalities and heterocycles with high enantioselectivity (up to >99:1 e.r.). Multi-gram scalability has been demonstrated along with catalyst recovery and recycling. ¹H NMR studies identified a 1400-fold rate enhancement under BIMP catalysis, compared to the prior state-of-the-art catalytic system. The utility of the aldol products has been highlighted with the synthesis of various enantioenriched building blocks and heterocycles, including 1,3-aminoalcohol, 1,3-diol, oxetane, and isoxazoline derivatives.     

Analysis of uncertainties in instantaneous soot volume fraction measurements using two-dimensional, auto-compensating, laser-induced incandescence (2D-AC-LII)

Laser-induced incandescence (LII) is an optical measurement technique capable of measuring soot volume fraction over a wide range of conditions. However, development of two-dimensional auto-compensating LII (2D-AC-LII) in the literature has been limited and until now, instantaneous measurements have not been demonstrated. In this paper, we successfully demonstrate instantaneous 2D-AC-LII soot volume fraction (SVF) measurements in an ethylene-air co-annular diffusion flame. Results were then used to support a detailed uncertainty analysis based on a Monte-Carlo simulation. Agreement between both the instantaneous and average SVF measurements with published data from attenuation measurements under identical conditions was found to be good. Uncertainties are discussed both in terms of an overall accuracy of the SVF measurement, which is strongly dominated by uncertainty in the optical properties of soot, and the comparative uncertainties with optical properties fixed. The uncertainty in an instantaneous 2D determination of SVF for a comparative measurement is dominated by photon shot noise, and in regions of high soot volume fraction it is below 25% (95% confidence interval). Shot noise uncertainty could be further reduced with additional pixel averaging at the expense of spatial resolution. This diagnostic shows significant promise for quantitative planar soot concentration measurements within turbulent flames.     

Asymmetric synthesis of (−)-(1R,7aS)-absouline

The most efficient and concise asymmetric synthesis of (?)-(1R,7aS)-absouline to date, which was accomplished in eight steps and 20% overall yield from commercially available starting materials, is described. The doubly diastereoselective conjugate addition of lithium (S)-N-benzyl-N-(α-methylbenzyl)-amide to an enantiopure α,β-unsaturated ester derived from l-proline was employed as the key step. Subsequent hydrogenolytic N-debenzylation and acid-promoted cyclisation of the resultant β-amino ester produced the 1-aminopyrrolizidin-3-one scaffold, then reduction with DIBAL-H was followed by DCC-mediated coupling with (E)-p-methoxycinnamic acid to complete the synthesis of (?)-(1R,7aS)-absouline.     

Concise and highly selective asymmetric synthesis of acosamine from sorbic acid

Diastereoselective conjugate addition of lithium (R)-N-benzyl-N-(α-methylbenzyl)amide to tert-butyl sorbate and subsequent chemo- and diastereoselective ammonium-directed olefinic oxidation of the resultant conjugate addition product {tert-butyl (3S,αR)-3-[N-benzyl-N-(α-methylbenzyl)amino]hex-4-ene} have been used as the key steps in a concise and highly selective asymmetric synthesis of the 2,3,6-trideoxy-3-aminohexose l-acosamine. This sequence of two chemical operations allows rapid assembly of the molecular architecture and facilitates the de novo asymmetric synthesis of methyl N,O-diacetyl-α-l-acosaminide in only 7 steps from commercially available sorbic acid in 15% overall yield.     

Lutetium gets a crown: Synthesis, structure and reaction chemistry of the separated ion pair complex, [Li(12-crown-4)2][(C5Me5)2LuMe2]

Reaction of (C₅Me₅)₂Lu(Me)(μ-Me)Li(THF)₃ (2) with excess 12-crown-4 affords the new separated ion pair complex, [Li(12-crown-4)₂][(C₅Me₅)₂LuMe₂] (3), in excellent yield. This complex reacts with 2,6-diisopropylaniline and phenylacetylene to give the methyl amide complex [Li(12-crown-4)₂][(C₅Me₅)₂Lu(Me)(NH-2,6-ⁱPr₂C₆H₃)] (4) and the bis(acetylide) complex [Li(12-crown-4)₂][(C₅Me₅)₂Lu(C≡C-Ph)₂] (5), respectively. Attempts to promote methane loss from complexes 3 and 4 to generate a lutetium methylidene or imido complex, respectively, were unsuccessful. The ability of the bis(acetylide) complex 5 to act as a π-tweezer complex was also explored. Reaction between [Li(12-crown-4)₂][(C₅Me₅)₂Lu(C≡C-Ph)₂] (5) and CuSPh gave only intractable lutetium products and the copper(I) species [Li(12-crown-4)₂][Cu(C≡C-Ph)₂] (8). The new lutetium complexes have been characterized by elemental analysis and NMR spectroscopy. Finally, the X-ray crystal structures of (C₅Me₅)₂Lu(Me)(μ-Me)Li(THF)₃ (2), [Li(12-crown-4)₂][(C₅Me₅)₂LuMe₂] (3), [Li(12-crown-4)₂][(C₅Me₅)₂Lu(Me)(NH-2,6-ⁱPr₂C₆H₃)] (4), [Li(12-crown-4)₂][(C₅Me₅)₂Lu(C≡C-Ph)₂] (5), and [Li(12-crown-4)₂][Cu(C≡C-Ph)₂] (8) are also reported.     

Holographic shaping of generalized self-reconstructing light beams

Bessel beams are an example of self-reconstructing (or self-healing) light beams. This property is useful in optical tweezers. Here we modify the Curtis-Koss-Grier algorithm [J.E. Curtis, B.A. Koss, D.G. Grier, Opt. Commun. 207 (2002) 169], which is frequently used in optical tweezers, to utilize the Fourier-space properties of such light beams for the construction of arbitrary self-reconstructing light beams. We demonstrate the performance of this algorithm using numerical simulations.